Online monitoring of polymerization inhibitors for control of undesirable polymerization

ABSTRACT

Disclosed herein are systems and methods for monitoring and controlling a nitroxide-based polymerization inhibitor in vinyl-based monomers. A dosage of the nitroxide-based polymerization inhibitor is provided in the vinyl-based monomers. A residual concentration of the nitroxide-based polymerization inhibitor is measured substantially in real time, and an optimized dosage of the nitroxide-based polymerization inhibitor is provided in response to the measured residual concentration.

TECHNICAL FIELD

This invention relates generally to systems and methods for the onlinemonitoring of polymerization inhibitors for control of undesirablepolymerization. More specifically, the invention relates to systems andmethods of monitoring and controlling a nitroxide-based polymerizationinhibitor in a vinyl-based monomer. The invention has particularrelevance to locally and/or globally monitoring and controllingundesirable polymerization in downstream petrochemical systems.

BACKGROUND

Many vinyl-based monomers are prone to spontaneous undesirablepolymerization during manufacturing and purification, as well as duringhandling, transportation, and storage. For example, the vinyl-basedmonomers can react under the heat used in manufacturing and purificationto undesirably form highly crosslinked polymers. These polymers may formfoamy or crusty granules that ultimately plug production lines andequipment, and thereby may potentially cause physical damage.

Nitroxide-based compounds can inhibit the undesirable polymerization ofvinyl-based monomers. In particular, nitroxide-based compounds can befast-acting inhibitors, and can be used alone or in combination withslower-acting polymerization retarders or antioxidants. To minimize theundesirable polymerization of the vinyl-based monomers, an optimizeddosage of nitroxide-based inhibitors may need to be continuouslyprovided into the liquid phase of the vinyl-based monomers duringmanufacturing and purification. There thus exists an ongoing need todevelop systems and methods of monitoring a residual concentration ofthe nitroxide-based inhibitors substantially in real time at any givenpoint in time so as to immediately provide an optimized dosage of thenitroxide-based inhibitor during a manufacturing process withoutinterruption.

SUMMARY

This disclosure accordingly provides systems and methods for monitoringand controlling a nitroxide-based polymerization inhibitor invinyl-based monomers, substantially in real time. The online monitoringof nitroxide-based inhibitor concentration can be correlated to anextent of undesirable polymerization. Moreover, the online monitoring ofnitroxide-based inhibitor concentration can be used as an indirect probeof additional factors affecting the overall polymerization kinetics,such as the dosage of secondary slower-acting polymerization retardersor antioxidants.

In an aspect, the invention provides a method of monitoring andcontrolling a nitroxide-based polymerization inhibitor in vinyl-basedmonomers. The method includes providing a dosage of the nitroxide-basedpolymerization inhibitor in the vinyl-based monomers. A residualconcentration of the nitroxide-based polymerization inhibitor ismeasured substantially in real time, and an optimized dosage of thenitroxide-based polymerization inhibitor is provided in response to themeasured residual concentration.

In another aspect, the invention provides a system for monitoring andcontrolling undesirable polymerization in vinyl-based monomers. Thesystem includes a fast flow sampling loop, and a control moduleconnected to the fast flow sampling loop. The control module is capableof controlling sample conditioning and measuring a residualconcentration of a nitroxide-based polymerization inhibitor in thevinyl-based monomers substantially in real time.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter that form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand the specific embodiments disclosed may be readily utilized as abasis for modifying or designing other embodiments for carrying out thesame purposes of the present invention. It should also be realized bythose skilled in the art that such equivalent embodiments do not departfrom the spirit and scope of the invention as set forth in the appendedclaims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of a system according to oneembodiment of the invention for monitoring and controlling a residualconcentration of a nitroxide-based inhibitor in vinyl-based monomers.

FIG. 2 is a schematic illustration of a system according to anotherembodiment of the invention.

FIG. 3 is a schematic illustration of a system according to yet anotherembodiment of the invention.

FIG. 4 is a schematic illustration of a fast flow sampling loop andcontrol module of the system of FIGS. 1-3.

FIG. 5 depicts the molecular structure of the nitroxide-based inhibitor(HTMPO) of FIGS. 1-3.

FIG. 6 is a graph plotting an ESR spectrum of the nitroxide-basedinhibitor of FIG. 5.

FIG. 7 depicts the molecular structure of the non-nitroxide retarder(Phenyl Quinone Methide).

FIG. 8 is a perspective view of an enclosure for the control module ofFIGS. 1-3.

FIG. 9 is a schematic illustration of a benchtop continuous stirred tankreactor configuration used to simulate the system of FIGS. 1-3.

FIG. 10 is a graph plotting a nitroxide signal response against run timeduring a calibration run in the configuration of FIG. 9.

FIG. 11 is a graph plotting a nitroxide signal against nitroxideconcentration in the configuration of FIG. 9.

FIG. 12 is a graph plotting a residual HTMPO concentration in theconfiguration of FIG. 9 run without retarders.

FIG. 13 is a graph plotting a residual HTMPO concentration and polymermake in the configuration of FIG. 9 run with and without retarders.

FIG. 14 is a graph plotting an ESR response and soluble polymermeasurements to temperature changes in the configuration of FIG. 9.

FIG. 15 is a graph plotting an ESR response and soluble polymermeasurements to changes in dosage, temperature, and residence time inthe configuration of FIG. 9.

DETAILED DESCRIPTION

Described herein are systems and methods for monitoring and controllinga nitroxide-based polymerization inhibitor in vinyl-based monomers,substantially in real time. The systems and methods can be advantageousin inhibiting undesirable polymerization. The system includes a fastflow sampling loop, an enclosure connected to the fast flow samplingloop, and a control module positioned within the enclosure. The controlmodule is capable of controlling sample conditioning and measuring aresidual concentration of a nitroxide-based polymerization inhibitor inthe vinyl-based monomers substantially in real time.

1. DEFINITIONS

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Preferred methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentinvention. All publications, patent applications, patents and otherreferences mentioned herein are incorporated by reference in theirentirety. The materials, methods, and examples disclosed herein areillustrative only and not intended to be limiting.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that do not precludethe possibility of additional acts or structures. The singular forms“a,” “and” and “the” include plural references unless the contextclearly dictates otherwise. The present disclosure also contemplatesother embodiments “comprising,” “consisting of” and “consistingessentially of,” the embodiments or elements presented herein, whetherexplicitly set forth or not.

Any ranges given either in absolute terms or in approximate terms areintended to encompass both, and any definitions used herein are intendedto be clarifying and not limiting. Notwithstanding that the numericalranges and parameters setting forth the broad scope of the invention areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical value, however,inherently contains certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.Moreover, for the recitation of numeric ranges herein, each interveningnumber therebetween with the same degree of precision is explicitlycontemplated. For example, for the range of 6-9, the numbers 7 and 8 arecontemplated in addition to 6 and 9, and for the range 6.0-7.0, thenumbers 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 areexplicitly contemplated.

As used herein, “monomers” refers to olefinic hydrocarbons, dienes,vinyl aromatic monomers, halogenated monomers, unsaturated acids,unsaturated esters, unsaturated amides, unsaturated nitriles,unsaturated ethers, acrylated urethanes, unsatured polyesters andmixtures thereof. For example, the monomers may include ethylene,propylene, 1,3-butadiene, chloroprene, butenes, isoprene, C4-C30α-olefins, styrene, α-methylstyrene, vinyltoluene, divinylbenzene,styrene sulfonic acid, 2,4-dichloro styrene, vinyl naphthalene,diisopropenyl benzene, vinyl chloride, acrylic acid, methacrylic acid,vinyl acetate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,trimethylolpropane triacrylate, polyethylene glycol diacrylate, methylmethacrylate, butyl methyacrylate, and structural isomers, derivativesof said compounds and mixtures thereof.

As used herein, “nitroxide-based inhibitor” refers to stable nitroxidefree-radical compounds (SNFR) having the generic structure:

where each R is alkyl or aryl and T is a group required to complete a 5-or 6-membered ring. For example, the nitroxide-based inhibitor mayinclude 4-hydroxyl-2,2,6,6-tetramethylpiperidine-1-oxyl or its4-substituted-2,2,6,6-tetramethylpiperidine-1-oxyl homologs. Likewise,the following corresponding hydroxyl amines or other homologs of theseSNFRs which could form an SNFR in situ are contemplated for use as anitroxide-based inhibitor.

Moreover, in some nitroxide-based inhibitors, two or more nitroxylgroups may be present in the same molecule by being linked through the Tmoiety as exemplified below where E is a linking group, such as diacids,diesters, diamides, diols, diamines, or triazines.

Furthermore, the nitroxide-based inhibitor may include the followingnitroxides: di-tert-butyl nitroxyl,1-oxyl-2,2,6,6-tetramethylpiperidine,1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol,1-oxyl-2,2,6,6-tetramethylpiperidin-4-one,1-oxyl-2,2,6,6-tetramethyl-4-n-propoxypiperidine,1-oxyl-2,2,6,6-tetramethyl-4-n-butoxypiperidine,1-oxyl-2,2,6,6-tetramethyl-4-t-butoxypiperidine,1-oxyl-2,2,6,6-tetramethyl-4-s-butoxypiperidine,1-oxyl-2,2,6,6-tetramethyl-4-(2-methoxyethoxy)piperidine,1-oxyl-2,2,6,6-tetramethyl-4-(2-methoxyethoxyacetoxy)piperidine,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl butyrate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylthexanoate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl octanoate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl laurate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4-tert-butylbenzoate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl succinate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate,1-oxyl-2,2,6,6-tetramethyl-4-allyloxy-piperidine,1-oxyl-2,2,6,6-tetramethyl-4-acetamidopiperidine,1-oxyl-2,2,6,6-tetramethyl-4-(N-butylformamido)piperidine,N,N′-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipamide,N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-caprolactam,N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-dodecylsuccinimide,2,4,6-tris-[N-butyl-N-(1-oxyl-2,266-tetramethylpiperidin-4-yl)]-s-triazine,2,4,6-tris-[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine,4,4′-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazin-3-one),1-oxyl-2,2,6,6-tetramethyl-4-(2,3-dihydroxypropoxy)piperidine,1-oxyl-2,2,6,6-tetramethyl-4-(2-hydroxyl-4-oxapentoxy)piperidine,derivatives of said compounds and mixtures thereof.

As used herein, “non-nitroxide-based polymerization retarder,”“non-nitroxide-based polymerization inhibitor,” or “non-nitroxide-basedantioxidant” refers to hindered phenols, quinones, hydroquinones,semi-quinones, catechols, tocopherols, quinone methides, aromatic nitrocompounds, aromatic nitroso compounds, aromatic N-nitroso compounds,oximes, hydroxylamines, aromatic diamines, diaromatic amines,non-nitroxide stable free radicals, thiazines, oxazines, and mixturesthereof.

The non-nitroxide-based polymerization retarder may include2,6-di-t-butylphenol, 4-alkyl-2,64-butylphenol, p-benzoquinone,o-benzoquinone, hydroquinone, hydroquinone methyl ether,t-butylcatechol, vitamin E,2-(3,5-Di-t-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)acetonitrile,2,6-di-t-butyl-4-(methoxymethylene)cyclohexa-2,5-dienone), and4-benzylidene-2,6-di-tert-butylcyclohexa-2,5-dienone, methyl2-(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)acetate,2-(3,5-di-t-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)acetic acid,nitrobenzene, nitrophenol, dintrophenol, 2,4-dinitto-6-s-butylphenol,2,4-ditro-o-cresol, nitrosobenzene, nitrosophenol, dinitrosophenol,dinitrosotoluene, nitrosophenylhydroxylamine, N,N-diethylhydroxylamine,1,1′-(hydroxyazanediyl)bis(propan-2-ol), N-isopropylhydroxylamine,p-phenylenediamine, N,N-dialkyl-1,4-phenylenediamine,N,N-diaryl-1,4-phenylenediamine, N-alkyl,N′-aryl-1,4-phenylenediamine,N,N-diphenyl amine, bis(4-octylphenyl)amine, galvinoxyl, diphenylpicrylhydrazyl, phenothiazine, phenoxazine, and structural isomers,derivatives of said compounds and mixtures thereof.

2. SYSTEM FOR MONITORING AND CONTROLLING A RESIDUAL CONCENTRATION OF ANITROXIDE-BASED INHIBITOR IN VINYL-BASED MONOMERS

In an aspect, the present invention is directed to a system formonitoring and controlling a residual concentration of a nitroxide-basedinhibitor in vinyl-based monomers. Referring to FIG. 1, the system 10 isin fluid communication with a monomer process column 12 and generallyincludes a fast flow sampling loop or sampling conditioning fast flowloop 14, and a control module or nitroxide-based inhibitor concentrationanalyzer (NCA) 18 connected to the fast flow sampling loop 14. Thecontrol module 18 controls initial dosage of nitroxide-based inhibitorinto the monomer process columns 12, measures residual concentration ofnitroxide-based inhibitor in the fast flow sampling loop 14, andprovides an optimized dosage of nitroxide-based inhibitor into themonomer process column 12 substantially in real time.

Referring to FIG. 2, a system 100 according to another embodiment of theinvention is schematically illustrated. The control module 18 in thisembodiment controls initial dosage of both nitroxide-based inhibitor andnon-nitroxide-based inhibitor into the monomer process column 12,measures residual concentration of nitroxide-based inhibitor in the fastflow sampling loop 14, which provides an indirect measure of thenon-nitroxide—based inhibitor residual, and provides an optimized dosageof both nitroxide-based inhibitor and non-nitroxide-based inhibitor intothe monomer process column 12 substantially in real time.

Referring to FIG. 3, a system 200 according to yet another embodiment ofthe invention is schematically illustrated. The control module 18 inthis embodiment is connected to a continuous stirred tank reactor (CSTR)20, although other structures performing the same function as the CSTR20 disclosed herein can be used instead. In the illustrated embodiment,the control module 18 controls initial dosage of non-nitroxide-basedinhibitor into the monomer process column 12, and collects a sampleslipstream into the CSTR 20 where it combines the sample slipstream witha dosage of nitroxide-based inhibitor. The control module 18 thenmeasures residual concentration of nitroxide-based inhibitor in thesample slipstream exiting the CSTR 20, which provides an indirectmeasure of the non-nitroxide-based inhibitor residual in the processstream and provides an optimized dosage of non-nitroxide-based inhibitorinto process stream substantially in real time.

The control module 18 is thus capable of measuring a residualconcentration of a nitroxide-based polymerization inhibitor in thevinyl-based monomers, and controlling sampling conditioning through theaddition of a nitroxide-based inhibitor in the monomer process columns12 (see FIGS. 1 and 2) or CSTR 20 (see FIG. 3), substantially in realtime. In some embodiments, the control module 18 is connected to thefast flow sampling loop 14 using stainless steel compression fittingssuch as, for example, available from Swagelok® in Solon, Ohio or Parkerin Columbus, Ohio. In other embodiments, however, the control module 18may be connected to the fast flow sampling loop 14 using any othersuitable fittings. Although in some embodiments the system 10, 100, 200may be a bench-top unit, the systems and methods described herein arenot limited in this regard.

Referring also to FIG. 4, the illustrated fast flow sampling loop 14 isdesigned to receive a process stream 22 through an inlet 26, obtain asample slipstream 30 from the process stream 22 as the process stream 22is running, and condition the sample slipstream 30 as desired beforeflowing it through the control module 18. For example, the sampleslipstream 30 may be filtered and the pressure and/or temperature may beadjusted before it flows through the control module 18. Thenitroxide-based inhibitor concentration of the sample slipstream 30 isdetermined by the control module 18, as explained below. After flowingthrough the control module 18, the sample slipstream 30 is returned tothe process stream 22 through an outlet 34. In the illustratedembodiment, the inlet 26, the control module 18, and the outlet 34 areall connected to a respective check valves 38 (e.g., nine in theillustrated embodiment) to facilitate moving the sample slipstream 30toward a predetermined direction and thereby prevent back pressure andcontamination via back flow into the process stream 22. In otherembodiments, however, the system 10, 100, 200 may include fewer than allof the check valves 38. In still other embodiments, the system 10, 100,200 may include additional valves and/or switches depending on the usagerequirements or preferences for the particular system 10, 100, 200.

In the illustrated embodiment, the control module 18 includes anelectron spin resonance (ESR) spectrometer or a miniaturized or microelectron spin resonance (μESR) spectrometer for analyzing the residualconcentration of a nitroxide-based polymerization inhibitor. In otherembodiments, however, the control module 18 may instead include or use agas chromatograph, a gas chromatograph-mass spectrometer, liquidchromatography, nuclear magnetic resonance, x-ray diffraction, x-rayfluorescence, atomic absorption, inductively coupled plasma emissionspectroscopy, an ultraviolet-visible spectrometer, an infraredspectrometer, a near-infrared spectrometer, a Raman spectrometer, afluorometer, a turbidimeter, dynamic light scattering, evaporative lightscattering, and/or a titrator. The systems and methods described hereinare not limited in this regard. In some embodiments, the polymer contentof the sample slipstream is determined separately using a peripheralmethod (e.g., evaporative light scattering) and correlated to theresidual concentration of nitroxide-based inhibitor. In otherembodiments, analytical techniques such as titration and turbidimetrymay allow for the direct measurement of the polymer content of thesample slipstream in conjunction with these embodiments.

In some embodiments, the control module 18 may further include a manualoperator or an electronic device having components such as a processor,memory device, digital storage medium, cathode ray tube, liquid crystaldisplay, plasma display, touch screen, or other monitor, and/or othercomponents. In certain instances, the control module 18 may be operablefor integration with one or more application-specific integratedcircuits, programs, computer-executable instructions, or algorithms, oneor more hard-wired devices, wireless devices, and/or one or moremechanical devices. Some or all of the control module 18 functions maybe at a central location, such as a network server, for communicationover a local area network, wide area network, wireless network, internetconnection, microwave link, infrared link, and the like. In addition,other components such as a signal conditioner or system monitor may beincluded to facilitate signal-processing algorithms. In someembodiments, the control module 18 can be coupled to any suitableprogrammable logic controller unit known in the art such as, forexample, LABView manufactured by National Instruments in Austin, Tex.

The illustrated ESR spectrometer measures electron resonance signals. Inthe ESR spectrometer, a sample of a chemical fluid is passed through aradio frequency (RF) or microwave source, while applying a slowlyvarying magnetic field. In some embodiments, a simple tube may serve asthe sample chamber. For example, the sample chamber may be formed out ofpolytetrafluoroethylene (PTFE) or quartz, and may have an inner diameterfrom about 3 mm to about 4 mm and an outer diameter from about 5 mm toabout 6 mm. Once the sample is received in the sample chamber, themagnetic field is rapidly modulated, and an ESR signal is derived. TheESR signal can indicate the presence of one or more free radicals ormolecules and molecular changes thereto in the chemical fluid sample. Asexplained below, the ESR spectrometer can further be tuned or calibratedto measure the concentration of free radicals in the chemical fluidpassed therethrough substantially in real time. In some embodiments, thecontrol module 18 may include a miniaturized ESR spectrometer such as,for example, available from Active Spectrum in Foster City, Calif. Inother embodiments, however, the control module 18 may include an ESRspectrometer of any other size. As detailed above, in still otherembodiments, the control module 18 may include any other sensors thatare capable of measuring a residual concentration of a nitroxide-basedpolymerization inhibitor substantially in real time.

Referring also to FIG. 5, the control module 18 may be tuned orcalibrated to have a substantially linear response to the concentrationof nitroxide-based polymerization inhibitors such as2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl (HTMPO). HTMPO is aworkhorse molecule used to inhibit undesirable or unwanted polymerformation in the petrochemical industry during manufacturing,processing, and storing of vinyl-based monomers. When passed through thecontrol module 18, the nitroxide-based inhibitor HTMPO can produce thethree-line ESR spectrum illustrated in FIG. 6. In other embodiments, thecontrol module 18 may be tuned or calibrated for any other suitablenitroxide-based polymerization inhibitors, such as, for example, the2,2,6,6-tetramethylpiperidyl-1-oxy radical. The systems and methodsdescribed herein are not limited in this regard.

In some embodiments, the integrated area under the ESR signal peaks (seefor example FIG. 6) has a substantially linear correspondence to theconcentration of the nitroxide-based inhibitor in the sample chamber inranges of about 1 ppb to about 10,000 ppm. In some embodiments, thelinear correspondence is provided to the concentration of thenitroxide-based inhibitor of about 1 ppb or more, about 2 ppb or more,about 3 ppb or more, about 4 ppb or more, about 5 ppb or more, about 6ppb or more, about 7 ppb or more, about 8 ppb or more, about 9 ppb ormore, about 10 ppb or more, about 11 ppb or more, about 12 ppb or more,about 100 ppb or more, about 200 ppb or more, about 300 ppb or more,about 400 ppb or more, about 500 ppb or more, about 600 ppb or more,about 700 ppb or more, about 800 ppb or more, about 900 ppb or more,about 1 ppm or more, about 10 ppm or more, about 20 ppm or more, about30 ppm or more, about 40 ppm or more, about 50 ppm or more, about 60 ppmor more, about 70 ppm or more, about 80 ppm or more, about 90 ppm ormore, about 100 ppm or more, about 200 ppm or more, about 300 ppm ormore, about 400 ppm or more, about 500 ppm or more, about 600 ppm ormore, about 700 ppm or more, about 800 ppm or more, about 900 ppm ormore, about 1,000 ppm or more, about 2,000 ppm or more, about 3,000 ppmor more, about 4,000 ppm or more, about 5,000 ppm or more, about 6,000ppm or more, about 7,000 ppm or more, about 8,000 ppm or more, or about9,000 ppm or more. In further embodiments, the linear correspondence isprovided to the concentration of the nitroxide-based inhibitor of about10,000 ppm or less, about 9,000 ppm or less, about 8,000 ppm or less,about 7,000 ppm or less, about 6,000 ppm or less, about 5,000 ppm orless, about 4,000 ppm or less, about 3,000 ppm or less, about 2,000 ppmor less, about 1,000 ppm or less, about 900 ppm or less, about 800 ppmor less, about 700 ppm or less, about 600 ppm or less, about 500 ppm orless, about 400 ppm or less, about 300 ppm or less, about 200 ppm orless, about 100 ppm or less, about 90 ppm or less, about 80 ppm or less,about 70 ppm or less, about 60 ppm or less, about 50 ppm or less, about40 ppm or less, about 30 ppm or less, about 20 ppm or less, about 10 ppmor less, about 9 ppm or less, about 8 ppm or less, about 7 ppm or less,about 6 ppm or less, about 5 ppm or less, about 4 ppm or less, about 3ppm or less, about 2 ppm or less, about 1 ppm or less, about 900 ppb orless, about 800 ppb or less, about 700 ppb or less, about 600 ppb orless, about 500 ppb or less, about 400 ppb or less, about 300 ppb orless, about 200 ppb or less, about 100 ppb or less, about 90 ppb orless, about 80 ppb or less, about 70 ppb or less, about 60 ppb or less,about 50 ppb or less, about 40 ppb or less, about 30 ppb or less, about20 ppb or less, about 12 ppb or less, about 11 ppb or less, about 10 ppbor less, about 9 ppb or less, about 8 ppb or less, about 7 ppb or less,about 6 ppb or less, about 5 ppb or less, about 4 ppb or less, about 3ppb or less, or about 2 ppb or less. This includes a substantiallylinear correspondence to the concentration of the nitroxide-basedinhibitor in a range of about 12 ppb to about 250 ppm. The ESRspectrometer can thus be calibrated to measure the concentration of freeradicals in the chemical fluid passed therethrough substantially in realtime.

In some embodiments, the control module 18 may be tuned or calibratedalso for non-nitroxide-based polymerization inhibitors or retarders, orantioxidants. Inhibitors or retarders typically offer protection fromundesirable polymerization during events such as unintended shutdownsresulting from power failures, where the fast-acting nitroxides would beconsumed quickly. During those events, the retarder would still persistand offer protection until further action can be taken. In someembodiments, the control module 18 may be calibrated fornon-nitroxide-based polymerization retarders such as phenyl quinonemethide(2,6-bis(1,1-dimethylethyl)-4-(phenylenemethylene)cyclohexa-2,5-dien-1-one),as illustrated in FIG. 7, phenols, hydroxylamines, and/or quinonemethides. For example, analytical techniques other than ESR spectroscopy(e.g., Gas Chromatography) may be used in conjunction with theseembodiments to directly measure the residual concentration of bothnitroxide-based inhibitors and non-nitroxide-based inhibitors.Additionally, ESR spectroscopy may be used in conjunction withspin-trapping agents to convert non-nitroxide-based inhibitors intoESR-detectable species. The systems and methods described herein are notlimited in this regard.

Referring also to FIG. 8, the control module 18 may be positioned withinan enclosure 50 for field installation in a vinyl-based monomermanufacturing facility. For example, the enclosure 50 may be a ClassI/Div II purge box or enclosure that includes a suitable purge system52, a relief valve 53, and a door 54. In other embodiments, theenclosure 50 may include any other box or enclosure of a suitably ruggedconstruction. The door 54 may optionally include a touchscreen mountedthereto for safe operation.

In some embodiments, the system 10, 100, 200 further includes anitroxide-based polymerization inhibitor dosing pump (not shown) that isconnected to the control module 18, which selectively activates thenitroxide-based polymerization inhibitor dosing pump. The undesirablepolymerization of the vinyl-based monomers can thus be controlled duringmanufacture and purification of the vinyl-based monomers. In furtherembodiments, the system 100, 200 further includes a non-nitroxide-basedretarder dosing pump. In other embodiments, however, dosages of thenitroxide-based polymerization inhibitor and/or the non-nitroxide-basedretarder may be provided using any other mechanisms. The systems andmethods described herein are not limited in this regard.

3. METHOD OF MONITORING AND CONTROLLING A RESIDUAL CONCENTRATION OF ANITROXIDE-BASED INHIBITOR IN VINYL-BASED MONOMERS

In an aspect, the present invention is directed to a method ofmonitoring and controlling a nitroxide-based polymerization inhibitor(e.g., 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl) in vinyl-basedmonomers. The method includes providing a dosage of the nitroxide-basedpolymerization inhibitor in the vinyl-based monomers. After the sampleslipstream 30 is conditioned in the fast flow sampling loop 14, thecontrol module 18 measures a residual concentration of thenitroxide-based polymerization inhibitor in the sample slipstream 30substantially in real time. In some embodiments, the residualconcentration is measured on a substantially continuous basis. In otherembodiments, however, the residual concentration may be measured on anon-continuous basis, e.g., in regular or irregular time intervals. Anoptimized dosage of the nitroxide-based polymerization inhibitor isprovided in response to the measured residual concentration. In someembodiments, the optimized dosage is so determined as to control anundesirable polymerization of the vinyl-based monomer during manufactureand purification thereof.

In some embodiments, the CSTR 20 resides after the fast flow samplingloop 14. The residual concentration of the nitroxide-based inhibitor canthen be measured from the contents of the CSTR 20, and the optimizeddosage of the nitroxide-based inhibitor can be provided into the CSTR20. While the control module 18 measures the residual concentration andprovides an additional optimized dosage of the nitroxide-basedinhibitor, the fast flow sampling loop 14 may be flushed or cleaned witha fresh process stream 26 prior to the next measurement.

In some embodiments, a degree of undesirable polymerization can beevaluated based on the measured residual concentration, as explainedbelow. For example, the degree of undesirable polymerization can beevaluated using at least one of an electron spin resonance spectrometer,a gas chromatograph, a gas chromatograph-mass spectrometer, liquidchromatography, nuclear magnetic resonance, x-ray diffraction, x-rayfluorescence, atomic absorption, inductively coupled plasma emissionspectroscopy, an ultraviolet-visible spectrometer, an infraredspectrometer, a near-infrared spectrometer, a Raman spectrometer, afluorometer, a turbidimeter, dynamic light scattering, evaporative lightscattering, and a titrator. In some embodiments, at least one of theco-dosed retarders may be non-nitroxide-based.

The present invention has multiple aspects, illustrated by the followingnon-limiting examples.

4. EXAMPLES

Tests simulating the polymerization of vinyl-based monomers in theprocess stream 22 during purification (via distillation) and manufacturewere conducted in a benchtop continuous stirred tank reactor (CSTR) 20(see FIG. 9). This test was a dynamic method that simulated the bottomor sump of a distillation column under continuous flow. Parameters ofthe process stream such as temperature, residence time through thereactor, and the inhibitor concentration could be varied during a runand process stream samples could be evaluated for effects. Styrene (withthe commercial inhibitor, tert-butyl catechol (TBC), removed) was chosenas a model vinyl-based monomer system, due to its attractivecharacteristics such as thermal auto-initiation and reproduciblepolymerization behavior. The temperatures (105° C.-120° C.) and therelative inhibitor and retarder dosages chosen for these runs wererepresentative of those typically encountered in the bottoms ofdistillation columns used in Styrene manufacture.

Example 1 Calibration

To establish the linearity of signal response of the control module 18to the concentration of nitroxide-based inhibitors, a calibration runwas conducted. Calibration solutions were prepared by dissolving2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl (HTMPO; see FIG. 5 formolecular structure) in toluene at concentrations ranging from 3.91 ppmto 250 ppm. These solutions were then flowed through the control module18 in order of increasing concentration at a rate of 1.5 mL/min at roomtemperature, and ESR spectra were collected continuously at intervals of47 sec/scan. At the end of the run, pure toluene was run through thecontrol module 18 to rinse out the last calibration solution from thesample chamber, and ESR spectra were also collected during this time.The double integral of the three line spectrum for HTMPO for each scan(see FIG. 6) was taken as the signal response and plotted against therun time during the calibration run (see FIG. 10). This plotdemonstrated the response of the control module 18 to changes in theconcentration of HTMPO. A calibration curve was constructed by plottingthe measured double integrals versus the HTMPO concentration of thecalibration solutions (see FIG. 11). This plot established that thesignal response of the control module 18 is highly linear to nitroxideconcentration with an r-squared of 0.9998.

Example 2 Simulation

Two runs were conducted at the same temperature and residence time,comparing the difference between dosing only a nitroxide-based inhibitorand dosing a combination of nitroxide-based inhibitor and non-nitroxideretarder. For the first run, Styrene was used with an initial dosage of25 ppm HTMPO as the model nitroxide-based inhibitor alone (see FIG. 12).In comparison, for the second run, Styrene was used with initial dosagesof 25 ppm HTMPO as the model nitroxide-based inhibitor and 200 ppmPhenyl Quinone Methide as the retarder (see FIG. 13). For both runs, theflow rate was set at 1.5 mL/min, which gave a residence time of 60 minin the CSTR 20, and the temperature of the CSTR 20 was set to 120° C.When this temperature was reached, ESR spectra were collectedcontinuously at intervals of 47 sec/scan for a four hour duration overwhich the residual concentration of HTMPO was measured. During thecourse of both runs, samples of the effluent exiting the control module18 were evaluated for soluble polymer content, which was representativeof the extent of undesirable polymerization.

For the inhibitor-only run, the nitroxide concentration decreased froman initial value of 25 ppm to a quantity below the detection limit,taken to be 0 ppm, over 37 minutes. This zero-value residual wasmaintained throughout the remainder of the four hour run. After theinhibitor was entirely consumed, the corresponding soluble polymerconcentration of the process stream drastically increased over the nextthree hours reaching a plateau in the last hour of around 80,000 ppm.

In contrast, for the inhibitor plus retarder run, the nitroxidedecreased from an initial value of 25 ppm to non-zero quantity of 0.7ppm over 45 minutes, and maintained this non-zero-value residual theremainder of the four hour run. The corresponding soluble polymerconcentration of the process stream increased significantly slower butsteadily over the next three hours reaching a much lower plateau in thelast hour of around 7,000 ppm.

Though not wishing to be bound by a particular theory, given that thetemperature, residence time, and initial nitroxide-based inhibitordosage were identical between the two runs, the only factor thataccounts for the considerably decreased rate and quantity of undesirablepolymerization (80,000 vs. 7,000 ppm) was the presence of a 200 ppminitial dosage of retarder. The non-nitroxide retarder was not detectedby the control module 18. However, its effect was detected by thenitroxide-based inhibitor residual as indicated by the longer time takento decay from the initial dosage of 25 ppm to a stable residual of 0.7ppm (45 vs. 37 min) and by the fact that a non-zero residual wasachieved under the same severity. These results revealed that thenitroxide-based inhibitor residual can be used as an indirect probe ofother undetected factors that can impact undesirable polymerization.

Example 3 Simulation

The process temperature was varied while keeping the initialinhibitor/retarder dosage and residence time constant. Styrene was usedwith initial dosages of 50 ppm HTMPO as the model nitroxide-basedinhibitor and 200 ppm Phenyl Quinone Methide(2,6-bis(1,1-dimethylethyl)-4-(phenylenemethylene)cyclohexa-2,5-dien-1-one;see FIG. 7) as a slower-acting retarder. The flow rate was set at 1.5mL/min, which gave a residence time of 60 min in the CSTR 20. Theinitial temperature of the CSTR 20 was set to 105° C., and when thistemperature was reached, ESR spectra were collected continuously atintervals of 47 sec/scan for a duration required to measure a stableresidual concentration of HTMPO. The temperature was then increased by5° C. (this increase in thermal severity raises the rate of undesirablepolymerization, thereby consuming more inhibitor and lowering theresidual), and then spectra were collected until a new stable residualconcentration of HTMPO was established. This procedure was performed twomore times until a final temperature of 120° C. was reached. Over thisperiod a stepwise drop in the residual HTMPO concentration was observedfor each 5° C. increase in temperature (see FIG. 14). These resultsdemonstrated the sensitivity of the control module 18 totemperature-induced changes in nitroxide-based inhibitor concentration.

Referring to FIG. 14, during the course of this run, samples of theeffluent exiting the control module 18 were evaluated for solublepolymer content, which was representative of the extent of undesirablepolymerization. Upon comparison, it was apparent that as the residualinhibitor concentration decreased with increasing temperature, thesoluble polymer content increased.

Example 4 Simulation

The process temperature, the inhibitor/retarder dosage, and theresidence time were varied. Again, Styrene was used with initial dosagesof 50 ppm HTMPO as the model nitroxide-based inhibitor and 200 ppmPhenyl Quinone Methide as the retarder. However, the initial flow ratewas set at 2.0 mL/min, which gave a residence time of 45 min in the CSTR20. The initial temperature of the CSTR 20 was set to 110° C., and whenthis temperature was reached ESR spectra were collected continuously atintervals of 47 sec/scan for a duration required to measure a stableresidual concentration of HTMPO. The temperature was then increased by5° C. to 115° C., and then spectra were collected until a new stableresidual concentration of HTMPO was established. Over this period astepwise drop in the residual HTMPO concentration was observed for theincrease in temperature (see FIG. 15). The dosage of the HTMPOnitroxide-based inhibitor was then increased to 100 ppm and the dosageof the Phenyl Quinone Methide retarder was increased to 400 ppm. Overthis period a stepwise increase in the residual HTMPO concentration wasobserved. The residence time was then increased to 60 min by loweringthe flow rate to 1.5 mL/min. Over this period a stepwise decrease in theresidual HTMPO concentration was observed for the longer residence timein the reactor. Finally the dosage of the HTMPO nitroxide-basedinhibitor was increased to 125 ppm and the dosage of the Phenyl QuinoneMethide retarder was increased to 500 ppm. Over this period a stepwiseincrease in the residual HTMPO concentration was observed. These resultsdemonstrated the sensitivity of the control module 18 to temperature-,residence time-, and dosage-induced changes in nitroxide-based inhibitorconcentration.

Referring to FIG. 15, during the course of this run, samples of theeffluent exiting the control module 18 were evaluated for solublepolymer content, which was representative of the extent of undesirablepolymerization. Upon comparison, a correlation between soluble polymerconcentration and residual inhibitor concentration was observed. As theresidual inhibitor concentration decreased with increasing temperature,the soluble polymer content increased. As the residual inhibitorconcentration increased with increasing dosage, the soluble polymercontent decreased, demonstrating the ability to control the degree ofundesirable polymerization by appropriately increasing the dosage ofinhibitor additive. As the residual inhibitor concentration decreasedwith increasing residence time the soluble polymer content increased,simulating that changes in process throughput (i.e., lower flow rate orhigher severity) can be detected by changes in the inhibitor residualconcentration. However, once again this increase in undesirablepolymerization could be controlled by increasing the dosage ofinhibitor/retarder, leading to an increased residual inhibitorconcentration and a decrease in the soluble polymer content.

It is understood that the foregoing detailed description andaccompanying examples are merely illustrative and are not to be taken aslimitations upon the scope of the invention, which is defined solely bythe appended claims and their equivalents.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While this invention may be embodied in many differentforms, there are described in detail herein specific preferredembodiments of the invention. The present disclosure is anexemplification of the principles of the invention and is not intendedto limit the invention to the particular embodiments illustrated.

Various changes and modifications to the disclosed embodiments will beapparent to those skilled in the art. Such changes and modifications,including without limitation those relating to the chemical structures,substituents, derivatives, intermediates, syntheses, compositions,formulations, or methods of use of the invention, may be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A method of monitoring and controlling anitroxide-based polymerization inhibitor in vinyl-based monomers, themethod comprising: providing a dosage of the nitroxide-basedpolymerization inhibitor in the vinyl-based monomers; measuring aresidual concentration of the nitroxide-based polymerization inhibitorsubstantially in real time; and providing an optimized dosage of thenitroxide-based polymerization inhibitor in response to the measuredresidual concentration.
 2. The method of claim 1, wherein the residualconcentration is measured on a substantially continuous basis.
 3. Themethod of claim 1 further comprising providing a fast flow samplingloop, and wherein the residual concentration of the nitroxide-basedinhibitor is measured after the fast flow sampling loop.
 4. The methodof claim 3, wherein after the fast flow sampling loop resides acontinuous stirred tank reactor and an apparatus for providing theoptimized dosage of the nitroxide-based inhibitor into the continuousstirred tank reactor and wherein the residual concentration of thenitroxide-based inhibitor is measured from the contents of thecontinuous stirred tank reactor.
 5. The method of claim 1 furthercomprising evaluating a degree of undesirable polymerization in thevinyl-based monomer based on the measured residual concentration.
 6. Themethod of claim 5, wherein the degree of undesirable polymerization isevaluated using at least one of an electron spin resonance spectrometer,a gas chromatograph, a gas chromatograph-mass spectrometer, liquidchromatography, nuclear magnetic resonance, x-ray diffraction, x-rayfluorescence, atomic absorption, inductively coupled plasma emissionspectroscopy, an ultraviolet-visible spectrometer, an infraredspectrometer, a near-infrared spectrometer, a Raman spectrometer, afluorometer, a turbidimeter, dynamic light scattering, evaporative lightscattering, and a titrator.
 7. The method of claim 5 further comprisingevaluating an effect of co-dosed retarders and/or antioxidants on thedegree of undesirable polymerization based on the measured residualconcentration.
 8. The method of claim 7, wherein the effect of theco-dosed retarders and/or the antioxidants is evaluated using at leastone of an electron spin resonance spectrometer, a gas chromatograph, agas chromatograph-mass spectrometer, liquid chromatography, nuclearmagnetic resonance, x-ray diffraction, x-ray fluorescence, atomicabsorption, inductively coupled plasma emission spectroscopy, anultraviolet-visible spectrometer, an infrared spectrometer, anear-infrared spectrometer, a Raman spectrometer, a fluorometer, aturbidimeter, dynamic light scattering, evaporative light scattering,and a titrator.
 9. The method of claim 8, wherein at least one of theco-dosed retarders is non-nitroxide-based.
 10. The method of claim 1,wherein the optimized dosage is so determined as to control anundesirable polymerization of the vinyl-based monomer during manufactureand purification thereof.
 11. The method of claim 1, wherein thenitroxide-based polymerization inhibitor includes2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl.
 12. The method of claim1, wherein the measured residual concentration is about 1 ppb to about10,000 ppm.
 13. A system for monitoring and controlling undesirablepolymerization in vinyl-based monomers, comprising: a fast flow samplingloop; and a control module connected to the fast flow sampling loop, thecontrol module being capable of controlling sample conditioning andmeasuring a residual concentration of a nitroxide-based polymerizationinhibitor in the vinyl-based monomers substantially in real time. 14.The system of claim 13, wherein after the fast flow sampling loopresides a continuous stirred tank reactor, and wherein the controlmodule is capable of measuring the residual concentration of thenitroxide-based inhibitor in the continuous stirred tank reactor. 15.The system of claim 13 further comprising a nitroxide-basedpolymerization inhibitor dosing pump that is connected to the controlmodule, wherein the control module selectively activates thenitroxide-based polymerization inhibitor dosing pump so as to controlthe undesirable polymerization of the vinyl-based monomers duringmanufacture and purification thereof.
 16. The system of claim 13 furthercomprising a non-nitroxide-based retarder dosing pump.
 17. The system ofclaim 13, wherein the nitroxide-based polymerization inhibitor includes2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl.
 18. The system of claim13, wherein the fast flow sampling loop is configured to obtain a sampleslipstream and to condition the sample slipstream before flowing theconditioned sample slipstream to the control module.
 19. The system ofclaim 18 further comprising a check valve that facilitates moving thesample slipstream toward a predetermined direction.
 20. The system ofclaim 13, wherein the measured residual concentration is about 1 ppb toabout 10,000 ppm.